Phenol adsorption and desorption with physically and chemically tailored porous polymers: Mechanistic variability...

Understanding phenol adsorption-desorption mechanisms allows adsorbent tailoring to improve capacity and adsorbent reuse. Amberlite™ XAD4, a commercial styrenic polymer that is convenient to physically and chemically modify, was functionalized with dimethylamine (DMA) or trimethylamine (TMA) and/or hyper-cross-linked with 1,2-dichloroethane. These modifications were applied to enhance individual and/or synergistic phenol adsorption mechanisms, including hydrogen bonding, electrostatic interactions, and π-π dispersion forces. While XAD4-DMA adsorbs more phenol at pH = 6, XAD4-TMA has 23% higher capacity at pH = 11 due to adsorbate deprotonation that increases electrostatic interactions. Combining hyper-cross-linking with amination maximizes adsorption capacity due to synergistic impacts associated with increased micropore volume and surface affinity. Amine groups reduce desorption efficiency by 6-94% due to stronger adsorbate-adsorbent interactions compared to π-π dispersion forces. Isobutanol, which forms hydrogen bonds, is the most efficient desorption solvent, followed by chloroform, which has the same polarity index but does not hydrogen bond. n-Hexane only desorbs phenol removed with π-π dispersion forces and is not appropriate to regenerate aminated polymers. 0.1 N NaOH is an environmentally benign solvent for regenerating as-received XAD4 and XAD4-DMA, but not XAD4-TMA. Understanding phenol adsorption mechanisms allows development of physiochemically modified polymers with increased phenol adsorption capacity and regeneration efficiency.